Tunable Covalent Organic Frameworks for the Light-induced Hydrogen Evolution Reaction

David Reyes-Mesa^a, Albert Gallego-Gamo^a, Axel Guinard^a, Adelina Vallribera^a, Albert Granados^a, Roser Pleixats^a, Carolina Gimbert-Suriñach^a

^aDepartment of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona, Spain

Proceedings of The Future of Hydrogen: Science, Applications and Energy Transition (H2Future)

Ibiza, Spain, 2024 April 17th - 19th

Organizers: Carolina Gimbert Suriñach, Sixto Gimenez Julia and Emilio Palomares

Contributed talk, David Reyes-Mesa, presentation 023
DOI: https://doi.org/10.29363/nanoge.hfuture.2024.023
Publication date: 27th February 2024

Generation of hydrogen through water splitting under visible-light irradiation has been a known topic for a long time now.^1,2 Photochemical water splitting is a complex process in which different components are required to fulfill the overall reaction, each of them having a key role including (i) harvesting the light, (ii) separation of charges, (iii) breaking and (iv) formation of chemical bonds.

Within the context of the hydrogen evolution half reaction (HER), a large range of inorganic semiconductor materials such as TiO₂ have been used,^1,3 thanks to their suitable electronic configuration and stability under photochemical conditions. However, limitations in solar to hydrogen efficiency hamper their implementation. On the other hand, organic semiconductors have more recently emerged as promising materials to be used in this field. Prominent examples of this family of semiconductors are 2D-covalent organic frameworks (COFs), which are reticular materials with high crystallinity and porosity.^4,5 They have been applied to photocatalysis including visible light-induced HER with great success.^6,7 One of the advantages of COF materials is their versatility to control chemical and electronic structure, allowing to rationally design better photocatalytic materials by enhancing solar light harvesting, charge separation, interaction with co-catalysts or dispersibility in water.⁸

In this work we have prepared and tested two families of 2D-COF materials under light-induced HER in combination with different co-catalysts. The organic skeleton of the organic semiconductors has been modified by adding moieties with different electron donor-acceptor properties to tune their light absorption capacities. This work also highlights the importance of having a well-known structure of the co-catalyst to improve the hydrogen production rate.

References:

[1] [1] Fujishima, A.; Honda, K. Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature 1972, 238, 37–38.

[2] [2] Zou, Z.; Ye, J.; Sayama, K.; Arakawa, H. Direct Splitting of Water under Visible Light Irradiation with an Oxide Semiconductor Photocatalyst. Nature 2001, 414, 625–627.

[3] [3] Chen, X.; Shen, S.; Guo, L.; Mao, S. S. Semiconductor-Based Photocatalytic Hydrogen Generation. Chem. Rev. 2010, 110, 6503–6570.

[4] [4] Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O’Keeffe, M.; Matzger, A. J.; Yaghi, O. M. Porous, Crystalline, Covalent Organic Frameworks. Science 2005, 310, 1166–1170.

[5] [5] Geng, K.; He, T.; Liu, R.; Dalapati, S.; Tan, K. T.; Li, Z.; Tao, S.; Gong, Y.; Jiang, Q.; Jiang, D. Covalent Organic Frameworks: Design, Synthesis, and Functions. Chem. Rev. 2020, 120, 8814–8933.

[6] [6] Vyas, V. S.; Haase, F.; Stegbauer, L.; Savasci, G.; Podjaski, F.; Ochsenfeld, C.; Lotsch, B. V. A Tunable Azine Covalent Organic Framework Platform for Visible Light-Induced Hydrogen Generation. Nat. Commun. 2015, 6, 1–9.

[7] [7] Biswal, B. P.; Vignolo-González, H. A.; Banerjee, T.; Grunenberg, L.; Savasci, G.; Gottschling, K.; Nuss, J.; Ochsenfeld, C.; Lotsch, B. V. Sustained Solar H2 Evolution from a Thiazolo[5,4-d]Thiazole-Bridged Covalent Organic Framework and Nickel-Thiolate Cluster in Water. J. Am. Chem. Soc. 2019, 141, 11082–11092.

[8] [8] Ghosh, S.; Nakada, A.; Springer, M. A.; Kawaguchi, T.; Suzuki, K.; Kaji, H.; Baburin, I.; Kuc, A.; Heine, T.; Suzuki, H.; Abe, R.; Seki, S. Identification of Prime Factors to Maximize the Photocatalytic Hydrogen Evolution of Covalent Organic Frameworks. J. Am. Chem. Soc. 2020, 142, 9752–9762

Acknowledgements:

This work is part of the MOLMATOSOL project (PID2021-128496OB-I00) funded by the MCIN/AEI/10.13039/501100011033/.

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